US 3996339 A
Method of reducing NO2 to NO with a granular mixture of ferrous sulfate and an alkaline hydrogen sulfate in a molar ratio of 3:1 to 1:1.
1. In a method for the chemical conversion of NO2 in a gas mixture to NO by reduction by passing the gas mixture through a container filled with an inorganic reducing composition, the improvement wherein said inorganic reducing composition is a mixture of ferrous sulfate and an alkali metal acid sulfate in a molar ratio of between 3:1 and 1:1.
2. The method of claim 1 wherein the inorganic reducing composition is applied to the surface of an inert carrier material.
The invention relates to an apparatus for chemical conversion of gas mixtures.
Such an apparatus comprising a container which has a gas inlet and a gas outlet and is filled with a granular reagent for maximum reaction surface area is described inter alia in U.S. Pat. No. 3,361,661.
In apparatus of this type a given constituent of a gas mixture is to be removed or to be converted, for example by reduction or oxidation. In the aforementioned patent specification the concentrations of ozone and of sulphur dioxide in a gas mixture are to be determined. Since in this determination the said constituents interfere with one another, in one analysis the ozone and in the other analysis the sulphur dioxide is removed. Ozone is removed in a container filled with granular ferrous sulphate heptahydrate (FeSO4.7H2 O).
Such an apparatus filled with ferrous sulphate may also be used for converting NO2 into NO.
It was found in practice that the said apparatus has disadvantages, for the conversion of NO2 into NO is not quantitative. In addition, the properties of the ferrous sulphate deteriorate at a comparatively rapid rate, because the ferrous sulphate is hydrolysed and because the NO2 is absorbed at the granular material.
It is an object of the present invention to provide a reagent for use in such an apparatus which has a long useful life and ensures complete conversion.
According to the invention an apparatus for the chemical conversion of gas mixtures which comprises a container having an inlet and an outlet and filled with a granular ferrous sulphate composition is characterized in that the composition is a mixture of ferrous sulphate and an alkali metal acid sulphate in a molar ratio from 3:1 to 1:1. These limits of the mixing ratio are critical; below 1:1 the reduction rapidly falls with increasing proportions of alkali metal acid sulphate. The upper limit of 3:1 is the limit of stability; at higher values hydrolysis occurs.
The said granular composition may be used as such, however, preferably a granular inert carrier material is used on the surface of which the mixture of ferrous sulphate and alkali metal acid sulphate is disposed.
The inert carrier material may be pumice, silica, quartz or polytetrafluoroethylene, preferably in a large-surface-area configuration.
The advantage of the apparatus according to the invention is that the desired conversions take place quantitatively while in addition the useful life is very long. The apparatus has a satisfactory mechanical strength, when the active material is disposed on an inert carrier its adherence is satisfactory, and the apparatus is capable of withstanding extreme conditions, such as large humidity and desiccation. It is effective even at room temperature and up to about 50° C.
It is permeable to SO2, NO, H2 S and mercaptanes, and it is not poisoned by sulphur compounds.
In a practical embodiment an apparatus according to the invention is filled with pumice having a grain size of 6 to 7 mesh (1 to 2 mm) and a specific surface area of from 100 to 200 m2 /g which is impregnated with a mixture of FeSO4.7H2 O and KHSO4 in a molar ratio of 1:1.
Impregnation is effected by wetting the grains in vacuo with a solution of the said salts and subsequent drying by evaporation.
At a temperature between 20° and 45° C the following reactions take place:
NO2 + 2FeSO4 + 2KHSO4 → NO + Fe2 (SO4)3 + K2 SO4 + H2 O
o3 + 2feSO4 + 2KHSO4 → O2 + Fe2 (SO4)3 + K2 SO4 + H2 O.
an embodiment of the invention will now be described, by way of example, with reference to the accompanying diagrammatic drawings.
FIG. 1 is a diagrammatic view of an apparatus according to the invention showing the reductor and oxidator in series with the source of NO2.
FIG. 2 is a diagrammatic view of a portion of the apparatus of the invention in which the reductor is in circuit with the source of NO2.
FIG. 3 is a diagrammatic view of a portion of the apparatus of the invention in which the reductor is in circuit with the source of NO2 and the oxidizes is in circuit with the reduced gas.
FIG. 4 is a curve showing NO2 content in the emerging gas stream for each of the three reductor-oxidizer combinations of the apparatus of the invention.
Referring now to FIG. 1, a gas stream 1 comprises pure air which is supplied at a rate of 150 cm3 /minute. A supply source which delivers gaseous NO2 at a rate of 0.065/μg/minute is indicated by 2. As a result, the gas stream contains 0.23 part of NO2 per million parts of air. A reductor 5 according to the invention and an oxidator 6 having a 100% oxidation efficiency can be arranged in series with the source of NO2 by three-way valves 3 and 4. The NO2 content in the emerging gas stream is determined by means of a coulometer 7. This coulometer does not determine the content of NO.
In the positions of the valves shown in FIG. 1 the air which issues from 2 and contains a metered amount of NO2 is measured. In the practical embodiment used a signal of 1.98 /μA was produced. FIG. 4 shows the output signal from the coulometer 7.
In the positions of the three-way valves shown in FIG. 2 the reductor 5 is in circuit. The NO2 is completely reduced to NO. The signal now becomes zero. Then the valves are set to the positions shown in FIG. 3. The reduced gas then is oxidised to become NO2 again. The signal 1.98/μA is again fully obtained, which proves that no absorption or other losses or the nitrogen oxide occur in the apparatus.
The reductor according to the invention was a tube of length 10 cm and diameter 13 mm. It contains 6 g of reducing agent, i.e. pumice grains of grain size from 1 to 2 mm to which 1 g of ferrous sulphate and 0.3 g of potassium hydrosulphate KHSO4 had been applied.
In the apparatus described the said reductor gave a yield of more than 99% for more than 1,000 hours.